JPH01266124A - Maleimide resin composition - Google Patents
Maleimide resin compositionInfo
- Publication number
- JPH01266124A JPH01266124A JP63094534A JP9453488A JPH01266124A JP H01266124 A JPH01266124 A JP H01266124A JP 63094534 A JP63094534 A JP 63094534A JP 9453488 A JP9453488 A JP 9453488A JP H01266124 A JPH01266124 A JP H01266124A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- maleimide
- epoxy resin
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000011256 inorganic filler Substances 0.000 abstract description 6
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 239000007822 coupling agent Substances 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 3
- 229920003986 novolac Polymers 0.000 abstract description 3
- 239000005011 phenolic resin Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000010680 novolac-type phenolic resin Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MFYNHXMPPRNECN-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine;phenol Chemical class OC1=CC=CC=C1.C1CCCCN2CCCN=C21 MFYNHXMPPRNECN-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- -1 dicumyl peroxide Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔概 要〕
マレイミド樹脂組成物に関し、
耐熱性、硬化性、耐クランク性等にすぐれたマレイミド
樹脂組成物を提供することを目的とし、基材樹脂として
、２０〜９０重量％の次式（Ｉ）により表わされるビス
マレイミド：
及び１０〜８０重景％の次式（Ｕ）により表わされるポ
リマレイミド：
（上式において、ｍは１〜６の整数を表わす）を組み合
わせて含み、かつ前記マレイミド１００重量部に対して
、
エポキシ樹脂 ２０〜６００重量部及び
フェノール系硬化剤 ５〜４００重量部を含むよう
に構成する。Detailed Description of the Invention [Summary] Regarding a maleimide resin composition, the purpose is to provide a maleimide resin composition with excellent heat resistance, curability, crank resistance, etc. A combination of bismaleimide represented by the following formula (I) in weight%: and polymaleimide represented by the following formula (U) in 10 to 80 weight%: (in the above formula, m represents an integer from 1 to 6) and 20 to 600 parts by weight of an epoxy resin and 5 to 400 parts by weight of a phenolic curing agent based on 100 parts by weight of the maleimide.
本発明はマレイミド樹脂組成物に関し、さらに詳しく述
べると、耐熱性、硬化性、耐クラツク性及び強靭性にす
ぐれたマレイミド樹脂組成物に関する。 本発明のマレ
イミド樹脂組成物は、上記したようなすぐれた性質を有
しているので、いろいろな分野において、特に多層積層
用樹脂、導電性ペースト、電子素子保護膜、接着剤、塗
料、封止材料および成形材料の分野で有利に用いること
ができる。The present invention relates to a maleimide resin composition, and more specifically, to a maleimide resin composition that has excellent heat resistance, curability, crack resistance, and toughness. Since the maleimide resin composition of the present invention has the excellent properties described above, it is used in various fields, particularly as a multilayer laminating resin, a conductive paste, an electronic device protective film, an adhesive, a paint, and a sealant. It can be used advantageously in the field of materials and molding materials.
近年、電子、電気機器、輸送機などの小型軽量化、高性
能化が進み、これに伴い耐熱性に優れた材料が望まれて
いる。BACKGROUND ART In recent years, electronics, electrical equipment, transportation equipment, etc. have become smaller, lighter, and more sophisticated, and along with this, materials with excellent heat resistance are desired.
耐熱性樹脂としてはポリイミド樹脂が一般に知られてい
るが、この樹脂は、脱水縮合型であるために、反応に伴
い生じる縮合水のために硬化物にボイドが発生しやすく
、また硬化物の信頼性を低下させる。一方、ポリイミド
自身は不溶、不融となるために成形が困難である。Polyimide resin is generally known as a heat-resistant resin, but since this resin is a dehydration condensation type, voids are likely to occur in the cured product due to condensation water generated during the reaction, and the reliability of the cured product may be reduced. Decreases sex. On the other hand, polyimide itself is difficult to mold because it is insoluble and infusible.
成形加工性を改良したポリイミドとしてビスマレイミド
およびポリマレイミド（架橋硬化型樹脂）が公知である
。しかし、ビスマレイミドは、高融点であるために、硬
化のために一般に高温で長時間（Ｉ８０〜３５０°Ｃ１
１５〜６０分）の時間を要するという欠点がある。また
、ポリマレイミドは、その硬化温度はビスマレイミドに
比バフ０〜８０℃程低いが、硬化物は架橋密度が高く、
ボロボロになったり、クランクが入り易いという欠点が
ある。また、ビスマレイミド及びポリマレイミドは、た
とえそれらを混合して使用しても、満足し得る硬化性を
保証することができない。さらにまた、公知の樹脂組成
物の場合、得られる硬化物が靭性に劣るということも障
害となっている。Bismaleimide and polymaleimide (crosslinked curable resin) are known as polyimides with improved moldability. However, since bismaleimide has a high melting point, it is generally cured at high temperature for a long time (I80~350°C1
The disadvantage is that it takes 15 to 60 minutes). In addition, although the curing temperature of polymaleimide is about 0 to 80°C lower than that of bismaleimide, the cured product has a high crosslinking density.
It has the disadvantage that it becomes tattered and the crank is easily inserted. Furthermore, bismaleimide and polymaleimide cannot guarantee satisfactory curability even when used in combination. Furthermore, in the case of known resin compositions, the fact that the resulting cured product has poor toughness is also a problem.
本発明の目的は、上記したような従来の技術の欠点を解
消すること、換言すると、種々の分野において有利に使
用することのできる、耐熱性、硬化性、耐クラツク性等
にすぐれたマレイミド樹脂組成物を提供することにある
。The purpose of the present invention is to eliminate the drawbacks of the conventional technology as described above. In other words, it is an object of the present invention to provide a maleimide resin with excellent heat resistance, hardenability, crack resistance, etc., which can be advantageously used in various fields. An object of the present invention is to provide a composition.
上記した目的は、本発明によれば、基材樹脂として、２
０〜９０重量％の次式（Ｉ）により表わされるビスマレ
イミド：
及び１０〜８０重量％の次式（ｎ）により表わされるポ
リマレイミド；
（上式において、ｍは１〜６の整数を表わす）を組み合
わせて含み、かつ前記マレイミド１００重量部に対して
、
エポキシ樹脂 ２０〜６００重量部及び
フェノール系硬化剤 ５〜４００重量部を含むこと
を特徴とするマレイミド樹脂組成物によって達成するこ
とができる。According to the present invention, the above-mentioned purpose is achieved by using 2 as the base resin.
0 to 90% by weight of bismaleimide represented by the following formula (I): and 10 to 80% by weight of a polymaleimide represented by the following formula (n); (In the above formula, m represents an integer of 1 to 6) This can be achieved by a maleimide resin composition that contains a combination of the following, and contains 20 to 600 parts by weight of an epoxy resin and 5 to 400 parts by weight of a phenolic curing agent based on 100 parts by weight of the maleimide.
本発明による樹脂組成物において、−ａ式（Ｉ）で表わ
されるビスマレイミド、−数式（ＩＩ）で表されるポリ
マレイミド、エポキシ樹脂及びフェノール系硬化剤を所
定の量で用いることが必須である。ビスマレイミドの劣
硬化性は、低融点であるポリマレイミドを添加すること
により改善され、ポリマレイミドによる硬化物のクラッ
ク性は、低架橋密度であるビスマレイミドを混合するこ
とにより解消される。また、新たにエポキシ樹脂を添加
することにより成形加工時の硬化性、作業性が改善され
る。エポキシ樹脂の硬化剤としてフェノール系硬化剤が
添加される。In the resin composition according to the present invention, it is essential to use -a bismaleimide represented by formula (I), -polymaleimide represented by formula (II), an epoxy resin, and a phenolic curing agent in predetermined amounts. . The poor curability of bismaleimide is improved by adding polymaleimide having a low melting point, and the cracking property of the cured product caused by polymaleimide is eliminated by mixing bismaleimide which has a low crosslink density. Further, by newly adding epoxy resin, curing properties and workability during molding are improved. A phenolic curing agent is added as a curing agent for the epoxy resin.
本発明の樹脂組成物は、さらに、次式（ＩＩＩ）により
表わされるブタジェン−アクリロニトリル共重合体を、
前記マレイミド樹脂１００重量部に対して５〜８０重量
部の量で有することができる：（上式において、ｎは２
〜１５の整数を表わす）。The resin composition of the present invention further includes a butadiene-acrylonitrile copolymer represented by the following formula (III),
It can be present in an amount of 5 to 80 parts by weight based on 100 parts by weight of the maleimide resin (in the above formula, n is 2
~15).
このブタジェン−アクリロニトリル共重合体は、通常可
撓剤として用いられているものであり、これを添加する
と、驚くべきことに、得られる硬化物の靭性が著しく高
められる。This butadiene-acrylonitrile copolymer is commonly used as a flexibilizing agent, and surprisingly, when it is added, the toughness of the resulting cured product is significantly improved.
本発明の樹脂組成物において、それを成形加工した後の
アフタキュアは、硬化物中の未硬化ビスマレイミドなど
の硬化反応を完結させるために、行うことが望ましい。In the resin composition of the present invention, it is desirable to carry out after-curing after molding it in order to complete the curing reaction of uncured bismaleimide and the like in the cured product.
本発明の樹脂組成物において、マレイミドのうちのビス
マレイミドの混合比は、２０〜９０％（重量％、以下％
は重量％を意味する）であることが望ましい。これは、
２０％以下では添加効果が現れず、また、組成物混合の
際は溶融混練等を用いるが、９０％を超えるとビスマレ
イミドの融点が高い影響が生じ、組成物の硬化性が悪く
なるためである。In the resin composition of the present invention, the mixing ratio of bismaleimide among maleimides is 20 to 90% (wt%, hereinafter %).
means weight %). this is,
If it is less than 20%, the effect of addition will not appear, and melt kneading is used when mixing the composition, but if it exceeds 90%, the melting point of bismaleimide will be high and the curability of the composition will deteriorate. be.
また、本発明の樹脂組成物において、マレイミドのうち
のポリマレイミドの混合比は、１０〜８０％であること
が望ましい。これは、１０％以下では添加効果が現れず
、８０％を超えると硬化物の架橋密度が掻めて高くなり
、クラックが入りやすくなるためである。Further, in the resin composition of the present invention, the mixing ratio of polymaleimide in maleimide is preferably 10 to 80%. This is because if the content is less than 10%, the effect of addition will not be apparent, and if it exceeds 80%, the crosslinking density of the cured product will become extremely high and cracks will easily occur.
さらにまた、本発明では、上記した通り、ブタジェン−
アクリロニトリル共重合体はマレイミド１００部（重量
部、以下部は重量部を意味する）に対して５〜８０部添
加することが望ましい、これは、５％以下では添加効果
が現れず、８０部を超えると硬化物表面にブタジェン−
アクリロニトリル共重合体がブリードアウトするからで
ある。Furthermore, in the present invention, as described above, butadiene-
It is desirable to add 5 to 80 parts of acrylonitrile copolymer to 100 parts (by weight) of maleimide. If exceeded, butadiene will be present on the surface of the cured product.
This is because the acrylonitrile copolymer bleeds out.
また、本発明において使用されるエポキシ樹脂としては
、ビスフェノールＡ型エポキシ樹脂、フェノールノボラ
ック型エポキシ樹脂、タレゾールノボラック型エポキシ
樹脂、ビスフェノールＦ型エポキシ樹脂、およびその他
のエポキシ樹脂をあげることができる。また、かかる樹
脂の添加量は、ビスマレイミドとポリマレイミドを合計
したマレイミド１００部に対して２０〜６００部である
ことが望ましい。２０部以下では添加効果が現れず、６
００部を超えるとマレイミドの効果を十分に引き出すこ
とが出来ないからである。Further, examples of the epoxy resin used in the present invention include bisphenol A epoxy resin, phenol novolac epoxy resin, Talesol novolac epoxy resin, bisphenol F epoxy resin, and other epoxy resins. Further, the amount of such resin added is preferably 20 to 600 parts per 100 parts of maleimide, which is the total of bismaleimide and polymaleimide. If it is less than 20 parts, the addition effect will not appear, and 6
This is because if the amount exceeds 0.00 parts, the effect of maleimide cannot be fully brought out.
エポキシ樹脂の硬化剤としては、−Ｓに用いられている
フェノール系樹脂をあげることができる。Examples of curing agents for epoxy resins include phenolic resins used in -S.
フェノール系硬化剤としては、フェノールノボラフ、ク
レゾールノボラックなどに代表されるノボラック型フェ
ノール樹脂、ビスフェノールＡなどが挙げられるが、こ
のなかで耐湿性の面からノボラック型フェノール樹脂が
好ましい。硬化剤の添加量としては、耐湿性、耐熱性、
機械特性などの面から、エポキシ樹脂１００部に対し２
５〜７５部が使用される。Examples of the phenolic curing agent include novolac type phenolic resins such as phenol novolaf and cresol novolak, bisphenol A, and the like, and among these, novolac type phenolic resins are preferred from the viewpoint of moisture resistance. The amount of curing agent added depends on moisture resistance, heat resistance,
From the viewpoint of mechanical properties, etc., 2 parts per 100 parts of epoxy resin
5 to 75 parts are used.
さらにまた、本発明によるマレイミド樹脂組成物には、
必要に応じて、以下の成分を任意に添加することができ
る：
（Ｉ）溶融シリカ、結晶シリカ、アルミナ、炭酸カルシ
ウムなどの粉末状の無機質充填材。無機質充填材の添加
量は組成物全体の３０〜８５−ｔ％の範囲にあることが
好ましい。この理由は、無機質充填材の添加量が３０−
ｔ％より少ないと添加効果が現れず、８５−ｔ％より多
いと流れ性の低下から、作業性が低下する可能性が生じ
るからである。Furthermore, the maleimide resin composition according to the present invention includes:
If necessary, the following components can be optionally added: (I) Powdered inorganic filler such as fused silica, crystalline silica, alumina, calcium carbonate, etc. The amount of inorganic filler added is preferably in the range of 30-85% of the total composition. The reason for this is that the amount of inorganic filler added is 30-
This is because if the amount is less than t%, the addition effect will not be exhibited, and if it is more than 85-t%, the flowability may be lowered, leading to a possibility that workability may be lowered.
（２）エポキシ樹脂と硬化剤との反応およびマレイミド
の硬化反応を促進させるための硬化促進剤。(2) A curing accelerator for accelerating the reaction between an epoxy resin and a curing agent and the curing reaction of maleimide.
硬化促進剤としては、２−メチルイミダゾールなどのイ
ミダゾール系、トリフェニルホスフィンなどのホスフィ
ン系、ＤＢＵのフェノール塩などのＤＢＵ （ジアザビ
シクロウンデセン）系、ジクミル−パーオキサイドのよ
うな過酸化物などが用いられる。Examples of curing accelerators include imidazole type such as 2-methylimidazole, phosphine type such as triphenylphosphine, DBU (diazabicycloundecene) type such as DBU phenol salt, peroxide such as dicumyl peroxide, etc. is used.
（３）無機質充填材を添加する場合、樹脂との相溶性を
向上させるための、カンプリング剤。例えば、３−アミ
ノプロピルトリエトキシシシラン等のシラン系カップリ
ング剤、あるいはテトラオクチルビス（ホスファイト）
チタネート等のチタン系カップリング剤などがあげられ
る。カップリング剤の添加量は、使用する無機質充填剤
の種類、量、比表面積およびカンプリング剤の最小被覆
面積にもよるが、本発明においては、０．１〜１５部が
好ましい。(3) Camping agent for improving compatibility with the resin when adding an inorganic filler. For example, silane coupling agents such as 3-aminopropyltriethoxysilane, or tetraoctylbis(phosphite)
Examples include titanium-based coupling agents such as titanates. The amount of the coupling agent added depends on the type, amount, specific surface area, and minimum coverage area of the inorganic filler used, but in the present invention, it is preferably 0.1 to 15 parts.
（４）離型剤としてのカルナバワックス、ステアリン酸
およびその金属塩、モンタンワックス等；難燃剤として
の臭素化エポキシ樹脂や、三酸化アンチモン等；顔料と
してのカーボンブランクなど。(4) Carnauba wax, stearic acid and its metal salts, montan wax, etc. as mold release agents; brominated epoxy resin, antimony trioxide, etc. as flame retardants; carbon blank, etc. as pigments.
本発明のマレイミド樹脂組成物は、以下に列挙した成分
を任意に組み合わせて、ロール、ニーダ−、エクストル
ーダー等の常用の手段を用いて、約６０〜８０℃の温度
で加熱混練することによって調製することができる。The maleimide resin composition of the present invention is prepared by combining any of the components listed below and heating and kneading the mixture at a temperature of about 60 to 80°C using a conventional means such as a roll, kneader, or extruder. can do.
本発明によるマレイミド組成物において、ビスマレイミ
ドは硬化物のクラック性を改善するために、ポリマレイ
ミドは硬化物の硬化性を改善するために、ブタジェン−
アクリロニトリル共重合体は硬化物の靭性を改善するた
めに、そしてエポキシ樹脂は成形加工時の硬化性、作業
性を改善するために、それぞれ作用する。In the maleimide composition according to the present invention, bismaleimide is used to improve the cracking properties of the cured product, and polymaleimide is used to improve the curability of the cured product.
The acrylonitrile copolymer works to improve the toughness of the cured product, and the epoxy resin works to improve the curability and workability during molding.
〔実施例〕
次いで、本発明をいくつかの実施例及び比較例について
説明する。その前に、これらの例において使用した原材
料をまとめて説明すると、次の通りである：
・ビスマレイミド：ビスマレイミド−３三井東圧■
・ポリマレイミド二式（ＩＩ）でｍ＝４のもの。[Examples] Next, the present invention will be explained with reference to some examples and comparative examples. Before that, the raw materials used in these examples are summarized as follows: - Bismaleimide: Bismaleimide-3 Mitsui Toatsu ■ - Polymaleimide of formula (II) with m=4.
・ブタジェン−アクリロニトリル共重合体：１１ｙｃａ
ｒ ＣＴＢＮ １３００
宇部興産■
・エポキシ樹脂：
タレゾールノボランク型エポキシ樹脂
エポキシ当量２００、軟化点７０℃
大日本インキ化学工業■エピクロンＮ−６６５・硬 化
剤：フェノールノボラック樹脂水酸基当量１０３、軟
化点８１ ”ｃ
大日本インキ化学工業■ ＴＤ−２１３１・硬化促進剤
ニジアザビシクロウンデセンサンアブロー 〇−ＣＡＴ
ＳＡ
・充 填 材ニジリカ粉末
龍森■ ＲＤ−８
１〜５ 、 六 １〜５
下記の第１表に記載の原材料を記載の量比で加圧双腕ニ
ーダで混練することにより組成物を調製した。また、試
験片の調製は以下のようにして行った：
まず、混練により得られた組成物を８メツシユパスのパ
ウダーとし、このパウダーをプレス金型に移し、１８０
℃、８０ ｋｇ ／ ｃｄにて１０分間圧縮成形したも
のをさらに２００℃、８時間の条件でアフターキュアし
た。・Butadiene-acrylonitrile copolymer: 11yca
r CTBN 1300 Ube Industries ■ Epoxy resin: Talesol novolank type epoxy resin Epoxy equivalent 200, softening point 70℃ Dainippon Ink & Chemicals ■ Epicron N-665 Hardening agent: Phenol novolac resin Hydroxyl equivalent 103, softening point 81 ”c Dainippon Ink & Chemicals ■ TD-2131/Curing accelerator Nidiazabicycloundecensanabrow 〇-CAT
SA ・Filling material Nijirica powder Tatsumori■ RD-8 1-5, 6 1-5 A composition is prepared by kneading the raw materials listed in Table 1 below in the amount ratios listed in a pressurized double-arm kneader. did. In addition, the test pieces were prepared as follows: First, the composition obtained by kneading was made into a powder of 8 mesh passes, this powder was transferred to a press mold, and 180
The material was compression molded at 80 kg/cd for 10 minutes at 200°C and after-cured for 8 hours.
上記のようにして得られた組成物について、特性評価を
以下のごとく行った：
・ガラス転移温度
熱機械分析装置（真空理工）にて測定。Characteristics of the composition obtained as described above were evaluated as follows: - Glass transition temperature measured using a thermomechanical analyzer (Shinku Riko).
・曲げ強度 ＪＩＳ Ｋ６９１１による。・Bending strength According to JIS K6911.
・クランク
成形冷却後の試料（ｌＯＸ５Ｘ３０ｍ）の断面を顕微鏡
にて、評価。- Evaluate the cross section of the sample (1OX5x30m) after crank molding and cooling using a microscope.
・硬化時間
試料約１ｇを熱販千上（Ｉ８０℃）に放置し、硬化する
までの時を測定。・Curing time Approximately 1 g of the sample was left in a heat oven (I80°C) and the time until it hardened was measured.
・５％
熱重量分析（ＴＧＡ）法により、試料の５％重重量減少
度を測定。・5% Measure the 5% weight loss of the sample using the thermogravimetric analysis (TGA) method.
得られた結果を次の第１表に示す。記載の結果、特に実
施例１〜５、および比較例１，２より、ビスマレイミド
とポリマレイミドの混合比はビスマレイミド２０〜９０
％、ポリマレイミドｌＯ〜８０％が良いことがわかる。The results obtained are shown in Table 1 below. From the results described, especially Examples 1 to 5 and Comparative Examples 1 and 2, the mixing ratio of bismaleimide and polymaleimide is 20 to 90% bismaleimide.
%, it can be seen that polymaleimide lO~80% is good.
また、比較例３より、添加するエポキシ樹脂は６００部
を超えると、硬化物のＴｇが低下し、さらに高温時の機
械的強度も低下することがわかる。Moreover, from Comparative Example 3, it can be seen that when the amount of epoxy resin added exceeds 600 parts, the Tg of the cured product decreases, and the mechanical strength at high temperatures also decreases.
以下余白
６〜１０ 、 六 １ Ｇ 〜 １０下記の
第２表に記載の原材料を記載の量比で加圧双腕ニーダで
混練することにより組成物を調製した。また、試験片の
調製は以ｒのようにして行った：
まず、混純により得られた組成物を８メソシユバスのパ
ウダーとし、このパウダーをプレス金型に移し、１８０
℃、８０ｋｇ／−にて１０分間圧縮成形したものをさら
に２００°Ｃ１８時間の条件でアフターキュアした。Margins 6 to 10, 61 G to 10 A composition was prepared by kneading the raw materials listed in Table 2 below in the proportions listed in a pressurized double-arm kneader. In addition, the test piece was prepared as follows: First, the composition obtained by mixing and purification was made into a powder of 8 mesoba, this powder was transferred to a press mold, and 180
The material was compression molded at 80 kg/- for 10 minutes at 200° C. and after-cured for 18 hours at 200° C.
上記のようにして得られた組成物について、特性評価を
以下のごと（行った：
・ガラス転移温度
熱機械分析装置（真空理工）にて測定。The properties of the composition obtained as described above were evaluated as follows: - Glass transition temperature was measured using a thermomechanical analyzer (Shinku Riko).
・曲げ強度 ＪＩＳ Ｋ６９１１による。・Bending strength According to JIS K6911.
・クラック
成形冷却後の試料（Ｉ０Ｘ５Ｘ３０ｍ）の断面を顕微鏡
にて、評価。- Evaluate the cross section of the sample (I0 x 5 x 30 m) after crack forming and cooling using a microscope.
・ブリードアウト性
成形冷却後の試料（Ｉ０Ｘ５Ｘ３０ｍｌ）の表面を目視
にて、評価。- Bleed-out property: Visually evaluate the surface of the sample (I0 x 5 x 30 ml) after molding and cooling.
・硬化時間
試料約１ｇを熱板上（Ｉ８０°Ｃ）に放置し、硬化する
までの時を測定。・Curing time Approximately 1 g of the sample was left on a hot plate (I80°C) and the time until it hardened was measured.
・５％重量減少点
熱重量分析（ＴＧＡ）法により、試料の５％重重量減湯
温を測定。・Measure the 5% weight loss water temperature of the sample using the 5% weight loss point thermogravimetric analysis (TGA) method.
得られた結果を次の第２表に示す。記載の結果、特に実
施例６〜１０、および比較例６．７より、ビスマレイミ
ドとポリマレイミドの混合比はビスマレイミド２０〜９
０％、ポリマレイミド１０〜８０％が良いことがわかる
。また、比較例８より、添加するエポキシ樹脂は６００
部を超えると、硬化物のＴｇが低下し、さらに高温時の
機械的強度も低下することがわかる。The results obtained are shown in Table 2 below. From the results described, especially Examples 6 to 10 and Comparative Example 6.7, the mixing ratio of bismaleimide and polymaleimide is 20 to 9.
It can be seen that 0% and 10 to 80% of polymaleimide are good. Also, from Comparative Example 8, the amount of epoxy resin added was 600
%, the cured product's Tg decreases and its mechanical strength at high temperatures also decreases.
比較例９．ｌＯより、ブタジェン−アクリロニトリル共
重合体の添加量はマレイミド１００部に対して、５部以
下では硬化物の靭性が向上せず、８０部を超えると硬化
物表面よりブリードアウトすることもわかる。Comparative example 9. From IO, it can be seen that if the amount of butadiene-acrylonitrile copolymer added is less than 5 parts per 100 parts of maleimide, the toughness of the cured product will not improve, and if it exceeds 80 parts, it will bleed out from the surface of the cured product.
以下余白
〔発明の効果〕
本発明によれば、ビスマレイミド及びポリマレイミドを
組み合わせて使用し、かつこれにエポキシ樹脂、フェノ
ール系硬化剤及び場合によりブタジェン−アクリロニト
リル共重合体を添加することにより、耐熱性、硬化性、
耐クラツク性、そして靭性にすぐれた樹脂組成物を得る
ことができる。Blank space below [Effects of the Invention] According to the present invention, by using a combination of bismaleimide and polymaleimide and adding an epoxy resin, a phenolic curing agent, and optionally a butadiene-acrylonitrile copolymer, heat-resistant properties, hardenability,
A resin composition with excellent crack resistance and toughness can be obtained.
Claims (1)
により表わされるビスマレイミド： ▲数式、化学式、表等があります▼（ I ） 及び１０〜８０重量％の次式（II）により表わされるポ
リマレイミド： ▲数式、化学式、表等があります▼（II） （上式において、ｍは１〜６の整数を表わす）を組み合
わせて含み、かつ前記マレイミド１００重量部に対して
、 エポキシ樹脂２０〜６００重量部 及び フェノール系硬化剤５〜４００重量部 を含むことを特徴とするマレイミド樹脂組成物。 ２、基材樹脂として、２０〜９０重量％の次式（ I ）
より表わされるビスマレイミド： ▲数式、化学式、表等があります▼（ I ） 及び１０〜８０重量％の次式（II）により表わされるポ
リマレイミド： ▲数式、化学式、表等があります▼（II） （上式において、ｍは１〜６の整数を表わす）を組み合
わせて含み、かつ前記マレイミド１００重量部に対して
、 次式（III）により表わされるブタジエン−アクリロニ
トリル共重合体： ▲数式、化学式、表等があります▼（III） （上式において、ｎは２〜１５の整数を表わす）５〜８
０重量部 エポキシ樹脂２０〜６００重量部 及び フェノール系硬化剤５〜４００重量部 を含むことを特徴とするマレイミド樹脂組成物。[Claims] 1. 20 to 90% by weight of the following formula (I) as the base resin
Bismaleimide represented by: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) and 10 to 80% by weight of polymaleimide represented by the following formula (II): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the above formula, m represents an integer of 1 to 6), and contains 20 to 600 parts by weight of an epoxy resin and 5 to 400 parts by weight of a phenolic curing agent per 100 parts by weight of the maleimide. A maleimide resin composition characterized by: 2. As the base resin, 20 to 90% by weight of the following formula (I)
Bismaleimide represented by: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) and 10 to 80% by weight of polymaleimide represented by the following formula (II): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the above formula, m represents an integer of 1 to 6) and is represented by the following formula (III) based on 100 parts by weight of the maleimide: ▲ Numerical formula, chemical formula, There are tables, etc. ▼ (III) (In the above formula, n represents an integer from 2 to 15) 5 to 8
A maleimide resin composition comprising 0 parts by weight of an epoxy resin and 20 to 600 parts by weight of an epoxy resin and 5 to 400 parts by weight of a phenolic curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63094534A JPH01266124A (en) | 1988-04-19 | 1988-04-19 | Maleimide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63094534A JPH01266124A (en) | 1988-04-19 | 1988-04-19 | Maleimide resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01266124A true JPH01266124A (en) | 1989-10-24 |
Family
ID=14112996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63094534A Pending JPH01266124A (en) | 1988-04-19 | 1988-04-19 | Maleimide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01266124A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8552123B2 (en) | 2010-03-24 | 2013-10-08 | Samsung Electronics Co., Ltd. | Thermosetting resin, composition including the same, and printed board fabricated using the same |
| JP2020026509A (en) * | 2018-08-17 | 2020-02-20 | 株式会社プリンテック | Resin composition and method for producing the same |
| US10994516B2 (en) * | 2017-09-07 | 2021-05-04 | Taiwan Union Technology Corporation | Resin composition, and pre-preg, metal-clad laminate and printed circuit board prepared using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55111035U (en) * | 1979-01-31 | 1980-08-04 | ||
| JPS5839347Y2 (en) * | 1979-08-22 | 1983-09-05 | 星崎電機株式会社 | Filter cleaning device for forced air-cooled condenser in refrigeration cycle equipment |
-
1988
- 1988-04-19 JP JP63094534A patent/JPH01266124A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55111035U (en) * | 1979-01-31 | 1980-08-04 | ||
| JPS5839347Y2 (en) * | 1979-08-22 | 1983-09-05 | 星崎電機株式会社 | Filter cleaning device for forced air-cooled condenser in refrigeration cycle equipment |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8552123B2 (en) | 2010-03-24 | 2013-10-08 | Samsung Electronics Co., Ltd. | Thermosetting resin, composition including the same, and printed board fabricated using the same |
| US10994516B2 (en) * | 2017-09-07 | 2021-05-04 | Taiwan Union Technology Corporation | Resin composition, and pre-preg, metal-clad laminate and printed circuit board prepared using the same |
| JP2020026509A (en) * | 2018-08-17 | 2020-02-20 | 株式会社プリンテック | Resin composition and method for producing the same |
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